Binary Distillation of Ethanol and Water:

Improvements to Steady-State Operation and Measurement

October 15, 1999

Group 3
Abstract
Due to problems in past years with the operating controls of the Rothfus Lab distillation column, the
focus of this study is to try and correct some of the issues associated with flowrates, Labview and tray
concentration measurement methods. In order to evaluate the condition of the distillation column at
steady state, accurate measurements of feed, distillate, reflux, and bottoms flowrates need to be easily
obtained. Improvements to the operation of the column include implementing control of parameters such
as the feed and reflux flow through rotameters, which are manipulated to achieve a state of equilibrium in
the column. A volumetric calibration of the boiler was made as well as calibration curves for each
rotameter to verify flowrates. A control system was implemented for bottoms, feed, and reflux
temperature. Step response data was taken and PID values were determined from Cohen-Coon tuning
algorithms; these were programmed into Labview software. Due to software problems, only the
proportional action of the controllers was functional. The boiler and reflux controls were effective;
however, the feed control was extremely poor. Two methods were used to estimate column tray
compositions: refractometry and T-xy diagram reading. A refractometer was used to examine the
refractive index of samples taken from the distillation column trays at steady state, and thus manually
determine its composition. A T-xy diagram was used to correlate tray temperatures output Labview and
ideal temperatures calculated from Chemsep to real and theoretical tray compositions. There was
considerable discrepancy between the compositions determined by the refractometer and T-xy diagram.
Based on previous studies, it may be suggested that the T-xy diagram is the better method to use in
determining tray compositions.

Perhaps you should mention if an azeotrope was present

Introduction
The purpose of this lab was to operate an eight stage binary distillation column of ethanol and water at
steady state. A number of issues are important in running a distillation column. Feed, distillate, reflux,
and bottoms flowrates are important to know for characterizing holdup, adjusting heaters, and measuring
output at different conditions. Composition of products and in each stage is similarly important,
especially in determining column effectiveness. And finally, methods for automatically controlling the
steady state operation of the column are of great interest since they relieve much of the burden of manual
adjustment. We improved the column setup by focusing on each of these three issues. We calibrated the
reflux and feed rotameters, found temperatures for steady state operation, and implemented temperature
control mechanisms. We also measured concentrations on each tray with a refractometer for comparison
with values from a theoretical Tx-y diagram. Our system of ethanol-water was safe for laboratory use.
The autoignition temperature of ethanol is 363 ºC; however, the column did not achieve temperatures
high enough to cause self-combustion during our use of it. It should be noted that while water
significantly decreases ethanol’s flammability, care should be taken to keep air out of the column since
ethanol is flammable at 13 ºC. We were careful not to introduce excess air to the column or expose it to
any flame sources.

Theory
Binary Distillation
Binary distillation is a unit operation commonly used to separate two-component mixtures. The basis for
separation is the difference in volatility of the two components. If the mixture is brought to a temperature
between the boiling points of the two components, two phases will be produced. Most of the more
volatile component will separate into the vapor phase while its less volatile counterpart will be
predominant in the liquid phase.

A Tx-y diagram illustrates the relationship between temperature and the corresponding vapor and liquid
compositions of the mixture at a given pressure. The relationship of water and ethanol in vapor-liquid
equilibrium at 1 atm can be seen in Figure 1.

T-X-Y Plot for ETHANOL and H2O

212.00 B
D

B Bubble Point
D Dew Point

204.00 B D

B D

196.00
emperature, F

B D
An azeotrope occurs when the vapor and liquid phases of a mixture have the same composition. As can
be observed in Figure 1, an azeotrope exists at T = 172.5 ºF. At this point, further separation of the
mixture with distillation is impossible because the vapor and liquid both have a composition of 80 mol%
ethanol and there is no driving force for mass transfer.

Relative volatility is used to characterize the tendency of one component to go into the vapor phase as
compared to another. It describes the degree of ease in separating the mixture; the greater the relative
volatility, the easier the separation. It is found by:

a ij = VPi / VP j (1)

where VPi and VP j are the vapor pressures of the two components i and j at a given temperature.

Distillation Column
A distillation column is a countercurrent series of flash stages in a stack of several sieve-like trays. A
reboiler at the bottom of the column operates at a temperature high enough to evaporate part of the
bottoms back to the column. At the top is a condenser that cools the vapor stream to saturated liquid. The
condensate is collected in a reservoir, some of which is refluxed back into the column. The amount of
condensate sent back to the column is given by the reflux ratio:

R=L/D (2)

where L is the amount of liquid returned to the column and D is the amount of overhead distillate being
removed. The vapor from the reboiler rises through the trays and mixes with the liquid coming down the
column from the condenser and the feed. Each of the individual trays acts like an equilibrium flash.
Vapor and liquid of different compositions enter, mix, and reach equilibrium; the mixture then separates
into two phases. The values of the exiting liquid and vapor compositions are predicted by the T-xy
diagram, as mentioned earlier.

In reality, the equilibrium assumption does not always hold. The level of deviation from equilibrium is
described by the Murphee tray efficiency, which is defined as:

? = (yn – yn+1) / (yn* - yn+1) (3)

where yn = actual vapor composition leaving stage n, yn+1 = actual vapor composition leaving stage n+1
(i.e. entering stage n), and yn* = the vapor composition in equilibrium with xn (actual liquid composition
leaving stage n).

Higher in the column, the vapor stream becomes richer in the more volatile component and leaner in the
less volatile component. Descending through the column the reverse is true as the liquid stream is stripped
of the more volatile component. The more volatile component tends to the top while the less volatile
Refractometer
Each material has a specific ability to refract light. A measure called the refraction index (RI) is used to
describe the degree to which a particular substance bends light. In a two-component mixture, the
refraction index generally lies somewhere between the refractive indices of each of the two components.
For instance, in our water-ethanol system (where ethanol has a higher RI than water does), the refractive
index increases as ethanol concentration rises.

By measuring the RI for several mixtures of known composition, one can prepare a calibration plot of RI
versus composition and use the plot to determine the composition of an unknown binary mixture with
experimentally determined RI.

Equipment & Procedure

The Hampden model fractional distillation column has seven trays plus a partial reboiler (Figure H.1).
The column also utilizes a total condenser, a feed preheater, and feed and reflux rotameters. The feed
enters the column at tray number 3. Utilizing the LabVIEW software, control of the heaters and pumps in
the column can be achieved, and temperature data for each tray can be recorded.

Steady State Operation

Before the overall column data was taken and analyzed, the column was brought to steady state. A feed
composition near 50 mole % ethanol was fed to the third tray. To bring the column to steady state, the
boiler was first set to 0.015 amps filled with approximately 3 liters of water. As the bottoms temperature
neared 180°F, the boiler was lowered to 0.008 amps. The feed flow was subsequently turned to a low
rate of approximately 40 mL/min, and the feed preheater was also turned to 0.012 amps. Once the feed
temperature leveled off at 180°F, a flow of 20 mL/min was refluxed, and the reflux heater was turned to
0.007 amps. These settings were maintained; this sequence allowed the column to reach steady state in
approximately 25 minutes.

Main Feed Rotameter Calibration

In order to calibrate the feed rotameter used in this experiment, the inlet feed pipe was disconnected from
the column and fitted with tubing to direct the flow. For this calibration, tap water was used (density of
ethanol/water mixture and water not significantly different). After turning on the feed pump, the
rotameter was manually set and maintained at a specific reading. Meanwhile, the actual flowrate was
measured using a stopwatch and graduated cylinder. This procedure was performed at incremental
rotameter readings of 20 to 70. The following data was collected: rotameter reading, ml water drained,
and time required. For this calibration, two trials were performed to produce the curve. To create the
calibration curve, volumetric flowrate (ml/s) is plotted against rotameter reading.

Reflux Rotameter Calibration

A similar procedure from above was followed for the calibration of the reflux rotameter. Since the
distillate chamber was already calibrated with volume markings along its axis, these markings were used
graduated cylinder and marked. With the column in steady state, these markings can then be used to
measure the bottoms stream over time.

Control Implementation
The column utilized three sources for heating streams: reboiler, feed preheater, and reflux heater. The
power rating for each of these was initially adjusted manually within LabView by controlling the
amperage to each. In order to better maintain steady state conditions, we developed a prototype control
system for boiler, feed, and reflux heaters.

Step response tests were performed on both the boiler heater and feed preheater. The column condition
was 40 mL/s feed flow rate with about 3 liters of solution in the boiler and a 0.5 reflux ratio. We first
waited for steady state with the boiler at 0.008 amps, feed preheater at 0.012 amps, and reflux heater at
0.007 amps. We then incremented boiler power to 0.015 amps and noted the response in bottoms
temperature over a period of about 7.5 minutes. We reset the boiler to 0.008 amps, set the feed preheater
to 0.010 amps, and waited for steady state. We subsequently increased the feed preheater to 0.015 amps
and noted the response in feed temperature for about 5 minutes.

Control implementation was performed within LabView software. Two VIs were modified: distillation.vi
and heaters.vi. To the former, we implemented an interface for each of the three heaters for switching
control on/off and entering PID values. To the latter, we added PID subroutines to each heater output
loop which could be turned on or off. The subroutines used the controlled temperature as process variable
and output a heater power value (amperage) in the range 0.000-0.016 amps. A value of 0.004 was added
to this output since the zero point of the heaters was at 0.004; the maximum heater power that the PID
could specify was thus 0.020 amps. Setpoint range limits were also incorporated into the PID
subroutines. These modifications were saved as two new files: distillation v2.vi and heaters v2.vi with the
v2 to indicate the second version. As per the proposal, the labels for the output file were identified and
are reported in Appendix H. The time increment problem in these programs was also corrected.

With the control programming in LabView, we attempted to bring the column to steady-state a number of
times. The procedure was the same for each time: we first set the boiler temperature to 193 ºF under
control and waited until it began to approach the setpoint. At that point, we turned on the feed flow and
set the feed temperature control to 166 ºF. When a steady distillate flowrate was achieved, reflux and
reflux temperature control was initiated at 165 ºF. The temperature of the reflux was set slightly below
that of the top column to achieve a saturated liquid.

Refractometer
The concentration on each tray can be measured using an Atago Hand Refractometer (see Figure H.2),
which provides a measurement of the indices of refraction through three adjustable scale readings which
range from 1.333 and 1.520. The Waters model gas chromatograph could also be used to measure the
tray concentrations, but it was inoperable due to technical limitations.

Prior to performing any solution test with the refractometer, it must first be calibrated with pure water at
Results and Discussion
Flow Calibration
Prior to our proposal and in past labs, the feed flowrate was provided through Labview. The values given
through Labview compared with the actual feed observed during operation provided evidence of the
inaccuracy of those measurements. The flow sensors used in correlation with Labview were not designed
to measure flowrate with the magnitude as small as that used during distillation of an ethanol/water
mixture. Initially, the flowrate was controlled by a relief valve located in the back of the distillation
setup. The orientation of the valve handle was noted and marked; in this position, steady state was
achieved. Due to the crudeness of this method and absence of functioning equipment, the current solution
to control and measure the feed flowrate was to install the rotameter already mounted to the column unit.
A calibration curve specific to this rotameter for the feed is provided below.

Main Feed Rotameter Calibration

Combined Trials
12
Volumetric Flowrate (mL/s)

10

y = 1.3046x
8 2
R = 0.9894
6

0
0 1 2 3 4 5 6 7 8
Rotameter Reading

Figure 2: Calibration Curve for Feed Rotameter. The fit of the data to the curve is good (R2=0.99). One data
point is set to (0,0) such that for a rotameter reading of zero, there should be no flow.

Although conversions are provided with the equipment to adjust rotameter readings to specified units
(mL/min), these additional calibration tests were performed to validate the given conversions. The
comparison between experimental values and those conversions provided with the equipment is shown in
 Reflux Rotameter Calibration
Combined Trials

1
Experimental
0.9
0.8
Equipment Specs

Volumetric Flow (mL/s)

0.7 y = 0.0061x
2
R = 0.9946
0.6 Linear
(Experimental)
0.5
Linear
0.4 (Equipment
y = 0.0052x
0.3 2
R = 0.9617
0.2
0.1
0
0 20 40 60 80 100 120 140 160
Rotameter Reading

Figure 3: Calibration Curve for Reflux Rotameter (Experimental and Equipment Specs). A slight deviation
exists between the measured volumetric flowrate and the given conversions. Both curves are anchored at (0,0).

The divergence of the experimental calibration curve to the given one may be due to possible wear of the
equipment. During the collection of data for the calibration, a stream of fluid was observed coming from
the base of the rotameter. This leak could have easily caused a decrease in the measured volumetric
flowrate, which is the discrepancy that has surfaced in figure 5.

Another problem confronted while trying to measure flowrate was a significant leak at the base of the
column between the bottom tray and the reboiler. The loose fitting between tray 7 and the reboiler allows
an excessive amount of fluid from the column to escape. Therefore, measurement of the bottoms flowrate
becomes difficult and unreliable.

In an attempt to collect some data to assess the condition of the column (despite all the problems), the
column was run and brought to “steady state,” where conditions including flowrate were recorded.
Equilibrium within the column was reached about 19 minutes following startup. At steady state and total
reflux, the feed was set at 2.61 ml/s (rotameter reading of 20), and the reflux at 0.21 ml/s (rotameter of
40), according to the calibration graphs presented above. The resulting bottoms flowrate was measured to
be about 0.17 ml/s. Data at steady state, including temperature profiles, is presented in Appendix B. The
Control Implementation
The results of the step response tests for the boiler and feed heater (Appendix C) were used to determine
first-order parameters, which are listed in Table 1. Cohen-Coon tuning relations (Appendix E) were used
to determine PID values for these heaters. For the reflux heater, time considerations prevented a step
response test; however, PID values were approximated from those for the feed heater. Because the reflux
heater is physically similar to the feed heater yet its flowrate is less, these PID values were made slightly
less than that for the feed heater. All of the PID values are listed in Table 2.

Table 1: First-order reaction curve parameters.

time constant τ (sec) gain Kp (°F/amp) delay θ (sec)
Boiler step response 377 1600 27
Feed preheater step response 62 1930 3

Table 2: PID parameters by the Cohen-Coon method.

Kc (F/amp) τI (sec) τD (sec)
Boiler heater 0.012 64.5 9.7
Feed heater 0.014 7.2 1.1
Reflux heater (approximated*) 0.01 6.0 1.0
*Reflux heater values not taken from step response data.

In the actual testing of the PID implementation, we found that the integral and derivative action in
LabView would not work. This problem was the focus of much attention during our runs of the column.
Its root, a relatively minor but obscure quirk of LabView, was only recently discovered and corrected.
However, our steady-state data reflects that of pure proportional controllers. As a result, there are steady-
state errors in each control loop as well as some low decay rates.

The boiler control was the most effective (Figures D.1 and D.2). The time to steady-state was short (6.7
minutes), the fluctuation at steady state of the boiler temperature was very low (±0.1 ºF), and the gain
error was only 0.6 ºF. The feed control was ineffective with a proportional controller (Figures D.3 and
D.4). The gain was too high and a large cyclic feed temperature pattern resulted (±25 ºF). When the gain
was decreased to observe effects, the cyclic pattern persisted and with greater gain errors. The reflux
control was reasonably effective (Figure D.5). Its gain error was 1.3 ºF and fluctuation at steady-state
was 0.7 ºF.

The feed flowrate varied throughout our runs on this column, and the initial PID values produced
consistent responses with no differences than those just described. Though exact numbers are not known
for all of our runs because the feed rotameter was being installed and calibrated, the feed flowrate was
between 10 and 100 mL/min. Effects of flowrate changes on control systems were calculated
theoretically rather than measured experimentally as initially proposed because of the rotameter issue and
time constraints. When modeled as stirred tanks, the heaters’Cohen-Coon PID values are not
significantly affected as shown in Appendix F. This confirms our observations that the control system
worked similarly despite flowrate differences. Our initial proposal suggested implementing an autotuning
occurred in the lower trays. The 0.5 °F temperature variation of the feed tray, tray 3, was the highest of
all the trays. This was probably due to irregular feed flow, which was visually observed as “spurts” from
the feed line. The low variation in the temperatures of the other trays confirmed that the column was at
steady state.

Samples from each tray, the distillate, the bottoms, and the feed were taken at this steady state. Their
compositions were analyzed using a refractometer. We then estimated the concentrations at each stage by
comparing the refraction index of the samples to our calibration curve (Figure G.1). As soon as the
mixture was drawn into the syringe at ambient temperature, the vapor in the syringe began to condensate.
This, of course, changed the compositions of the solutions, which gave us biased results. Furthermore,
the refractometer was dependent on user accuracy since the refraction index must be read from a
manually adjusted scale. Tray concentrations may also be determined by using tray temperatures from
Table A.1 in the Appendix to read data points from the Tx line of the T-xy diagram. Tray concentrations
estimated by the refractometer calibration curve and T-xy diagram are in Table 3.

Table 3. Estimated Ethanol Concentrations by Tray

Tray Refractometer T-xy concentration, "Real" T-xy concentration, Ideal
RI Concentration (Based on Labview output) (Based on Chemsep temperatures)
Bottoms 1.3332 0 0.02 0.02
1 1.3335 0 0.025 0.09
2 1.3337 0 0.04 0.125
3 1.341 0.2 0.12 0.14
4 1.342 0.22 0.08 0.15
5 1.341 0.2 0.125 0.16
6 1.35 0.42 0.13 0.17
Distillate 1.364 1 0.21 0.2

As can be seen in Table 3, there was a significant (30-60%) disparity between concentration values
determined from the refraction index. Assuming that the T-xy diagram is an acceptable means to
determine distillation tray concentrations (Koch et al., 1998), the discrepancy between concentrations
based on RI and those based on the T-xy diagram suggests that the refractometer is unsuitable for
measuring tray concentrations. However, this does not mean that the T-xy diagram is foolproof; it was
assumed that the overall column pressure was 1 atm, while in reality, there may have been a pressure
gradient. We assumed that with a small temperature gradient, the pressure gradient from the top to the
bottom of the column was also small, and the effect of pressure on the T-xy diagram was negligible.

Conclusions
The purpose of this exploration was to address flowrate control, Labview issues, and measurement of tray
and product concentrations to provide calibrated reflux and feed rotameters, temperatures for steady state
Flowrate Calibration
Further steps need to be taken in order to obtain more accurate flowrate readings for the column. First
and foremost, the leaks that are present at the base of the reflux rotameter and the column should be fixed.
Once this is done, additional data points for the reflux rotameter calibration should be collected, and the
resulting curve compared to that given with equipment’s set specifications. In order to increase the
significance of the curves derived in this study, further calibration trials should be performed for each
rotameter. One option to bypass the work outlined above is to replace the rotameters and implement
appropriate flow sensors to be translated into Labview. This method of measuring would probably be
more effective and consistent than relying on manual adjustments of the rotameters.

Control
There are a number of directions for future development of control of the column. First, since the integral
and derivative action of the column have just now been implemented, the performance of the column
under true PID control can be evaluated. Stability should be much greater under this control. Second,
there might be a way to link the setpoint temperature of the reflux stream to the temperatures at the top of
the column so that the reflux truly enters as a saturated liquid. This would involve a number of checks to
filter bad thermocouple data and to make sure the column is running at steady state versus start-up.

Finally, a manual autotuning procedure should used to compare to step response data. It would be
performed on a heater by first increasing the gain to a very high number and setting the derivative and
integral actions to zero; this would alternate the heater control variable between its two range extremes
(0.004 and 0.020 amps) depending on the sign of the error. A limit cycle would occur, from which the
ultimate gain and period could be used in a Ziegler-Nichols tuning scheme for PID parameters.

Tray Concentrations
To obtain more accurate readings of the distillation tray concentrations, alternative methods to the
refractometer should be used. A suitable method that is readily available in the laboratory is gas
chromatography. Distillation tray concentrations determined via the gas chromatograph are generally
within ±0.07 the values determined by a T-xy diagram (Koch et al., 1998). While there has been a
considerable amount of exploration into composition and temperature relationships for ethylene glycol
and water (Fox et all, 1997), it may be of interest to draw similar correlations for ethanol-water systems.

Did you consider measuring the efficiency of the column.

This can be done by using the Macabe-Thiel method to
calculate the number of theoretical plates. This can then
be compared to the actual number of plates to determine
the efficiency. I know this was not the purpose of the
experiment but it would be interesting to see what kind of
numbers you get. Again, the refractometer method needs
to be improved before this can be done.

All in all this report was easy to read and presented in an

organized format. I had difficulty fully understanding the
LabView control software but that is not a big deal since I
References
1. ‘Operation Instructions for the Fractional Distillation Column’, Hampden Eng. Corp., 1993.
2. Biegler L.T., Grossman I.E., & Westerburg A.W. Systematic Methods of Chemical Process Design.
New Jersey: Prentice Hall, 1993.
3. Fox, Stephen, Altug Koymen, Kendra McCoy. “Separation of Ethylene Glycol and Water in a
Distillation Tower” Carnegie Mellon University, 1997.
4. Geankopolis, Christine J. Transport Processes and Unit Operations. New Jersey: Prentice Hall,
1993.
5. Koch, Eric, Jeff Linwood, Adam Madigan, Tobin McDaniel. “Distillation: Binary Mixture of
Ethanol-Water” Carnegie Mellon University, 1998.
6. Prieve, D. Lecture Notes, Unit Operations, 06-202, Fall 1998.
7. Reid, R.C., Prausnitz, J.M., & Sherwood, T.K. The Properties of Gases and Liquids, 2nd Edition.
New York: McGraw-Hill, 1987.
8. Unit Operations Laboratory Reports. Fall, 1997, 1998.
Appendices

A: Steady-state operation of the column without control and R=0.5 .................................................... 13

B: Steady-state operation of the column under control and total reflux ............................................... 15
C: Step response curves ...................................................................................................................... 16
D: Controlled column data.................................................................................................................. 17
E: Cohen-Coon tuning ........................................................................................................................ 20
F: Control modeling............................................................................................................................ 20
G: Refractometer calibration curve ..................................................................................................... 22
H: Data output key.............................................................................................................................. 22
H: Equipment ..................................................................................................................................... 23
Appendix A: Steady-state operation of the column without control and R=0.5

Note: The theoretical predictions made for temperatures in the column were developed from ChemSep
software running a binary system of ethanol and water. The following specifications were input:
Murphee efficiency of 0.8, 0.5 mol fraction EtOH in the feed, feed at 183.2 F, boiler temperature at 204.5
F, reflux ratio of 0.5, and column pressure of 1.2 atm. The following models were used in the
thermodynamic package: Gamma-Phi K model, Original UNIQUAC mode, Soave-RK Cubic EOS,
Antoine Vapour pressure, Excess Enthalpy.

Table A.1: Temperature profile 1 hour 18 minutes after start-up.

tray number temperature (F) tray number temperature (F)
bottoms 204.5 4 189.3 (183.8)
1 202.4 (188.4) 5 187.3 (183.1)
2 196.1 (185.2) 6 184.8 (182.4)
3 187.9 (184.2) 7 181.5 (181.7)
feed 183.2
Temperatures in parentheses are those predicted by ChemSep.

210

205

200

195
temperature (F)

190

185

180

175
actual
theoretical
170
bottoms 1 2 3 4 5 6 7
 Steady-State Operation of Column: Excerpt
210

205

200

temperature (F)
195

boiler
190 bottoms
tray 1
tray 2
tray 3
185 feed
tray 4
tray 5
180 tray 6
top

175
4050 4070 4090 4110 4130 4150 4170
time (s)
Figure A.3: Column temperatures at steady state. Most temperatures showed less than 0.5 °F varation. Noise in
tray 3, the feed tray, was probably due to irregular feed flow.
Appendix B: Steady-state operation of the column under control and total reflux

Table B.1: Temperature Profile 18.8 minutes after start-up.

tray number temperature (F) tray number temperature (F)
bottoms 199.8 4 189.8
1 196.7 5 185.4
2 195.3 6 180.3
3 193.7 7 176.1
feed 190.2

205

boiler
200
tray 1
tray 2
195 tray 3
tray 4
temperature (F)

190
tray 5

185
tray 6

180 tray 7

175

170
1000 1020 1040 1060 1080 1100 1120 1140 1160 1180 1200
time after start-up (s)

Figure B.2: Temperature profile at total reflux. Steady-state was difficult to reach at total reflux, as seen by the
changing temperatures in the column. The temperatures in the upper part of the column appear to be decreasing and
becoming closer together.
Appendix C: Step response curves

216 0.016

214 0.014

0.012

bottoms temperature (F)

212

boiler power (amps)

0.01
210
0.008
208
0.006
(t − θ)
Tf − T −
τ
=e
206 T f − Ti τ = 377 s
0.004
T f − Ti θ = 27 s
= Kp
∆Pboiler K p = 1600 °F/amp
204
K p e − θs 0.002
Gp =
τs + 1

202 0
-100 0 100 200 300 400
time (s)

Figure C.1: Step response curve for boiler. The boiler power was increased 0.007 amps and bottoms temperature
was monitored. The resulting response appears first-order.
204 0.016

202 0.014

0.012
200

feed preheater (amps)

feed temperature (F)

0.01
198
0.008
196 (t − θ)
Tf − T −
=e τ 0.006
T f − Ti
τ = 61.9 s
194 T f − Ti
= Kp θ = 3.1 s 0.004
∆Ppreheat
− θs K p = 1930 °F/amp
K pe
192 Gp =
τs + 1 0.002
Appendix D: Controlled column data

250 0.025

200 0.02

boiler temperature (F)

boiler power (amps)

150 0.015

100 0.01

50 0.005

boiler
boiler power
0 0
0 200 400 600 800 1000 1200 1400
time (s)

Figure D.1: Control of boiler temperature. Boiler temperature was controlled using a proportional gain of 0.012
amp/ºF and a setpoint of 193 ºF. Control was started at the beginning of start-up and it took 6.7 minutes to reach
99% of the boiler steady-state value of 192.4 ºF.
193 0.025

192.8

192.6 0.02

192.4
boiler temperature (F)

boiler power (amps)

192.2 0.015

192

191.8 0.01

191.6

191.4 0.005
 200 0.05

180 0.045

160 0.04

feed heater power (amps)

140 0.035

feed temperature (F)

120 0.03

100 0.025

80 0.02

60 0.015

40 0.01

20 feed 0.005
feed heater power
0 0
275 475 675 875 1075 1275 1475
time (s)

Figure D.3: Control of feed temperature. Feed temperature was controlled using a proportional gain of 0.014
amp/ºF and a setpoint of 166 ºF. Control of the feed was started 4.6 minutes after that of the boiler, taking 1.3
minutes to reach 99% of its steady-state value of 163.7 ºF.

190 0.03

180
0.025

170
0.02
feed temperature (F)

feed power (amps)

160

0.015

150

0.01
140

0.005
130
 165 0.03

164 0.025

reflux heater power (amps)

reflux temperature (F)
163 0.02

162 0.015

161 0.01

160 0.005

reflux
reflux heater power
159 0
5400 5450 5500 5550 5600 5650 5700 5750 5800 5850 5900
time (s)

Figure D.5: Steady-state control of reflux temperature. Reflux was controlled using a proportional gain of 0.01
amp/ºF and a setpoint of 165 ºF. The controlled stream had a temperature of 163.6±0.7 ºF. Heating was necessary
because reflux was supercooled in the condenser and needed to be returned to saturation temperature.
Appendix E: Cohen-Coon tuning

Given a first-order process with a gain of K, a time constant of τ, and a delay of θ, PID parameters may be
calculated by the Cohen-Coon approximation:

1 τ 4 θ 
Kc =  + 
K θ  3 4τ 
32 + 6θ τ
τI = θ (4-6)
13 + 8θ τ
4
τD = θ
11 + 2θ τ

Appendix F: Control modeling

For each of the heaters in the distillation column (boiler, feed, and reflux), it is convenient to develop
models based on a continuously stirred tank with a heat input. The boiler is essentially a CST. Though
the feed and reflux heaters are more similar to heat exchangers, the CST model is used because of its
simplicity and absence of partial derivatives. These models assume no phase change. In reality, the
heaters in the distillation column do cause phase change; however, for calculating general trends for use
in PID parameters, these simple models are sufficient. The models also assume that the mass in the tank
and the fluid flowrate through are constant. This is appropriate to a column running at steady-state.

For a continuously stirred tank with a mass flowrate of fluid m, mass holdup of M, inlet and outlet
temperatures T0 and T, and heat input of Q, the following energy balance may be written:

dT
mC p (T0 − T ) + Q = MC p (7)
dt

When this is rewritten and simplified in the Laplace domain, the following equation results:

Kp 1 M
T ( s) = Q( s) where K p = ,τ= (8)
1 + τs mC p m

The useful aspect of this modeling is the inverse proportionality of the process gain and time constant to
m. As the flowrate of the fluid through the heater increases by a factor of x, the gain and time constants
decrease by 1/x. Since control parameters in Cohen-Coon tuning are developed from these latter two
constants, the effects of flowrate changes on PID tuning values are easily calculated.
Table F.1: Modeled effects of flowrate on PID constants.
boiler feed
feed Kp τ θ Kc τI τD Kp τ θ Kc τI τD
mL/min F/amp sec sec F/amp sec sec F/amp sec sec F/amp sec sec
10 6400 1508 27 0.0117 66.0 9.79 7720 248 3 0.0143 7.35 1.09
20 3200 754 27 0.0117 65.5 9.75 3860 124 3 0.0143 7.31 1.09
30 2133 503 27 0.0118 65.0 9.72 2573 83 3 0.0144 7.27 1.08
40 1600 377 27 0.0118 64.5 9.69 1930 62 3 0.0144 7.24 1.08
50 1280 302 27 0.0118 64.0 9.66 1544 50 3 0.0144 7.20 1.08
60 1067 251 27 0.0119 63.6 9.63 1287 41 3 0.0145 7.17 1.08
70 914 215 27 0.0119 63.2 9.60 1103 35 3 0.0145 7.13 1.07
80 800 189 27 0.0119 62.7 9.57 965 31 3 0.0145 7.10 1.07
90 711 168 27 0.0120 62.3 9.54 858 28 3 0.0146 7.06 1.07
100 640 151 27 0.0120 61.9 9.51 772 25 3 0.0146 7.03 1.07

The table above shows that for flowrates of 10-100 mL/min through the boiler or feed, the PID constants
Kc, τI, and τD vary little. The gains on both, which is the primary contributor to stability, vary a maximum
of 3% on this range. Since this flowrate range is representative of typical flows that the boiler or feed
might experience, the model’s prediction is that the PID constants need not be changed based on the
column flowrate conditions.
Appendix G: Refractometer calibration curve

1.365

1.36

1.355

Refraction Index
1.35

1.345

1.34

1.335

1.33
0 0.2 0.4 0.6 0.8 1 1.2
Volumetric Concentration

Figure G.1: Refractometer calibration curve.

Appendix H: Data output key

The tab-delimited data file that the distillation program produces does not include labels. The following
is a key to its columns. Unlabelled column numbers have not yet been identified or defined.

column # description
1 17 tray 2 temperature
2 18 bottoms temperature
3 19 top (tray 7) temperature
4 20 feed heater temperature
5 21 reflux heater temperature
6 boiler temperature (ºF) 22
7 feed temperature 23
8 reflux temperature 24
9 distillate temperature 25
Appendix H: Equipment

Figure H.1. Hampden Distillation Column

 DISTILLATION:
ENERGY BALANCE ON THE
CONDENSER

SaKeithia Mason
Mitesh Master
Meredith Welsh
ABSTRACT

In this experiment we write an energy balance for an ethanol and water distillation
column. We calculate the flow rate of the distillate produced by the condenser through
batch distillation. Lab VIEW measures the inlet and outlet temperature of the cooling
water. Using this data, we close the energy balance equation around the condenser.
Lastly, we plot a T-xy diagram to assess flammability and to determine the reboiler
explosion temperature.
TABLE OF CONTENTS

INTRODUCTION 1
BACKGROUND: SAFETY DATA 1
ENERGY BALANCE CALCULATIONS 4
RESULTS 6
CONCLUSIONS 11
REFERENCES 13
INTRODUCTION

Distillation is a common industrial method used for separation. In this lab, a simple
batch distillation column of ethanol and water runs at steady state. The Hampden
distillation column (reference Binary Distillation of Ethanol and Water) is comprised of a
total condenser, a feed preheater, and feed and reflux rotameters. In this experiment, we
allow the ethylene glycol and water mixture to distill through the column. The condenser
produces distillate that flows into a collection vessel. Before measurements began, we
stabilize the column at steady state. After distillate forms at a constant rate, we collect
distillate and timed how long it takes for the distillate to reach a lesser volume. Further
calculations are then needed to complete the energy balance.

BACKGROUND: SAFETY DATA

We want to assess the likeliness of an explosion of ethanol-water mixture in our reboiler

because the reboiler uses a spark to heat the bottoms. If the bottoms level drops below the
insert point of the spark, there is risk of an explosion. This analysis examines what vapor
composition is necessary to cause an explosion.

In the reboiler, there exists a vapor-liquid phase equilibrium dependant upon the
temperature and pressure. For our analysis, we are assuming that the pressure is close to
one atmosphere. Since this is a two-component system with differing vapor pressures,
there will be differing compositions in the liquid and vapor mixtures.

Our sensors can detect the temperature of the bottoms. We are assuming that the bottoms
temperature does not change very much with vertical position, thereby allowing us to
make the vapor temperature the same as the measured temperature in the bottoms. Once
we know this along with T-xy data, we can feed the temperature data into the attached
MathCAD module and see what the vapor composition of the ethanol will be. Embedded
below is our MathCAD module. Feel free to enter different T-xy data and various
temperatures by double clicking on the insert.

Once we have this data, we can compare it to our flammability data give in Figure 1 and
see if combustion is likely.

1
 Note that this module only works for (near) constant pressure. Please be wary of this.
Attempt to use Txy data that has plenty of values at the limits for a better fit.

 0   0   387.1  Instructions:
 0.1  0.711  324.2
      1) Uncheck "automatic calculation" in the
 0.2   0.868   292.2  Math menu.
 0.3   0.926   272.2 
      2) Enter tabular data for Txy-diagram here.
 0.4   0.955   257.6  If you need more or fewer rows use the
xes :=  0.5  yes :=  0.972  Tes :=  246.5  "matrix" tool (View-Toolbars-Matrix).
 0.6   0.982   237.39
      3) All other parameters are entered next to
 0.7   0.989   229.8  the Txy diagram at the very end of this
 0.8   0.994   223.19 document. You can move there end now
 0.9   0.997   217.3  by pressing Ctrl-End.
  
 1   1   212.1 

This MathCAD module allows us to enter either temperature and the liquid or vapor
composition for the given component and returns the other two pieces of information.
Click on the module within the Word file to experiment with collected data.

Given the vapor mole fraction of the water-ethanol mixture, one can determine the water
and ethyl alcohol volume percent. With this, one can now examine the graph below and
see if flammable conditions exist.

2
Figure 1: Limits of Flammability of Ethyl Alcohol-Water Vapor-Air Mixture at 100ºC and Atmospheric
Pressure

With this information, we can assess the likeliness of ethanol vapor flammability.

3
ENERGY BALANCE CALCULATIONS
Here we base the calculations for our cooling water energy balance on a very narrow
point in time. Because of this, we are able to assume that all of our values are constant
over this range. The temperatures we use are the temperatures of the inlet (To) and
outlet (T) cooling water streams. All temperatures are in K.

To := 294.977 T := 301.973

The flowrate of the cooling water is constant over time. For this run, in L/min, our flowrate
is as follows:

Vcw := 2.588

Next, we use the heat capacity of water at the operating temperature of the condenser to
calculate how much energy enters the cooling water from the distillate. This correlation is
based on the To and T values of the water, as well as the enthalpy coefficients specific to
water, A, B, C, and D. Also necessary is R, given in J/mol*K.

−4 −6 − 10
A := 7.7010 B := 4.595⋅ 10 C := 2.452110
⋅ D := −8.59⋅ 10

T
τ := R := 8.314
To τ = 1.024

Cpw := R⋅ A +

B
⋅ To ⋅ ( τ + 1) +
C 2. (2
⋅ To ⋅ τ + τ + 1 + ) D 
2 3 2
 τ⋅ To 
Cpw = 66.983

Now we calculate the change in enthalpy, ∆ H, in J/mol.

∆H := Cpw⋅ ( T − To )

∆H = 468.611

To find the total heat exchanged, we must also take the flowrate of the cooling water into
account. To include this in our calculation, we need the molecular weight of water
(MWw), in g/mol, and the density of water ( ρ), in g/L. The resulting value, ∆ Q is the total
heat entering the cooling water per time, and is shown here in watts.

MWw := 18.015 ρw := 998

Vcw⋅ ∆H⋅ ρw
∆Qcw :=
MWw

4 ∆Qcw 3
∆Qcw = 6.719 × 10 ∆Q := ∆Q = 1.12 × 10
60

4
Throughout the run, we also calculate the average volumetric flow rate of the distillate.
This value (Vd) is in L/min.

Vd := .03848

In order to calculate the amount of heat that leaves the distillate in the condenser, we
first need to know the heat capacity of the mixture. Here we use a correlation to
calculate Cp (values A, B, C, and D) with respect to T and To and the percent
compositions by mass ( µme, µmw). R is given in J/mol*K, resulting in Cd in J/mol*K
as well.

µwe := .95 µme := .88 Ae := 2.1530 Aw := 7.7010

µww := .05 µmw := .12

−2 −4
Be := 5.113⋅ 10 Bw := 4.595⋅ 10

T
τ := R := 8.314 −5 −6
To Ce := −2.004⋅ 10 Cw := 2.452110
⋅

τ = 0.814 − 10 − 10
De := 3.280⋅ 10 Dw := −8.59⋅ 10

Cde := R⋅ Ae +

Be
⋅ To ⋅ ( τ + 1) +
Ce 2. (2
⋅ To ⋅ τ + τ + 1 + ) De 
2 3 2
 τ⋅ To 

Cde = 140.828

5
 RESULTS

From the collected LabVIEW data, we plot the following graphs. We fitted trend lines
and use the equations in the time dependent calculations.

Cooling Water Flowrate

Series1 Linear (Series1)

4.5

3.5

3
Flowrate (L/min)

y = 2E-06x + 2.5826
2.5

1.5

0.5

0
970 1170 1370 1570 1770 1970 2170 2370 2570 2770
Time (s)

Figure 2. Flow rate versus time.

Figure 3. Temperature of distillate versus time.

Temperature of Distillate

Series1 Poly. (Series1)

80

79.5

y = 3E-07x2 + 0.0002x + 76.392

79
Temperature of Distillate

78.5
(degrees F)

78

77.5

77

76.5
970 1170 1370 1570 1770 1970
Time (s)
2170 2370 2570 2770
6
 Temperature of Tray 6

Series1 Poly. (Series1)

208

206

y = -2E-06x2 + 0.0139x + 180.43

204

202
Temperature of Tray 6
(degrees F)

200

198

196

194

192

190
970 1170 1370 1570 1770 1970 2170 2370 2570 2770
Time (s)

Figure 4.Temperature of tray 6 versus time.

Temperature of Outlet Cooling Water

Series1 Log. (Series1)

85.5

85

84.5

84
Temperature of Cw(out)
(degrees F)

83.5

83

y = 2.6887Ln(x) + 63.613
82.5

82

81.5

81
970 1170 1370 1570 1770 1970 2170 2370 2570 2770
Time (s)

Figure 5. Temperature of outlet cooling water versus time.

Temperature of Inlet Cooling Water

Series1 Poly. (Series1)

71.8

71.6

71.4
Temperature of Cw(in)

71.2
(degrees F)

71

y = -1E-07x2 + 0.0007x + 70.413

70.8

70.6

70.4
970 1170 1370 1570 1770 1970 2170 2370 2570 2770
Time (s)

Figure 6. Temperature of inlet cooling water versus time.

7
Below in Table 1, we calculated the distillate flow rate. These flow rates vary with time.
However, they are not used in our calculations with respect to time dependence because
the calculated flow rates are not taken with respect to time. The following table shows
how variable the flow rate is.

Table 1. Flow rate calculation of the distillate.

Trial Volume (mL) Time (min.sec) Flow rate (mL/min)
1 250 5.34 45.2
2 200 5.14 38.31
3 250 6.56 36.08
4 150 4.23 34.33

8
Now, by substituting the equations depicting time dependency into the equations in
place of the constants we used previously, we are able to perform the entire calculation
for any point in time, once the column is running. The only two variables that we use as
time dependent are the cooling water inlet and outlet temperatures. Here, t must be
entered in seconds.

t := 2370

To :=
5 (
⋅ −1⋅ 10
−7 2
⋅ t + .0007t + 70.413 − 32 + 273.15 )
9

5
T := ⋅ ( 2.6887ln
⋅ ( t) + 63.613 − 32) + 273.15
9

The flowrate of the cooling water is constant over time.

Vcw := 2.588

Heat capacity:

−4 −6 − 10
A := 7.7010 B := 4.595⋅ 10 C := 2.452110
⋅ D := −8.59⋅ 10

T
τ := R := 8.314
To τ = 1.024

Cpw := R⋅ A +

B
⋅ To ⋅ ( τ + 1) +
C 2. (2
⋅ To ⋅ τ + τ + 1 +) D 
2 3 2
 τ⋅ To 
Cpw = 66.986

Enthalpy:

∆H := Cpw⋅ ( T − To )

∆H = 483.628

Total heat entering per time:

MWw := 18.015 ρw := 998

Vcw⋅ ∆H⋅ ρw
∆Qcw :=
MWw

4 ∆Qcw 3
∆Qcw = 6.934 × 10 ∆Q := ∆Q = 1.156 × 10
60

9
Again, here we use the equations depicting time dependency to calculate the heat
leaving the distillate at any point in time.

t := 2370

To :=
5 (−2⋅10− 6⋅t2 + .0139t + 180.43 − 32) + 273.15
9

T :=
5 (
⋅ 3⋅ 10
−7 2 )
⋅ t + .00002t + 76.392 − 32 + 273.15
9

Due to the nature of our measurements for the distillate flow rate, we are unable to
calculate this with respect to time. Although we know that the flow changes with time,
we perform this calculation with the average value.

Vd := .03848

Heat capacity:
Note that for this calculation that we assume the composition of the distillate is not
changing.

µwe := .95 µme := .88 Ae := 2.1530 Aw := 7.7010

µww := .05 µmw := .12

−2 −4
Be := 5.113⋅ 10 Bw := 4.595⋅ 10

T
τ := R := 8.314 −5 −6
To Ce := −2.004⋅ 10 Cw := 2.452110
⋅

τ = 0.813 − 10 − 10
De := 3.280⋅ 10 Dw := −8.59⋅ 10

Cde := R⋅ Ae +

Be
⋅ To ⋅ ( τ + 1) +
Ce 2. (2
⋅ To ⋅ τ + τ + 1 + ) De 
2 3 2
 τ⋅ To 

Cde = 140.985

10
 Cdw := R⋅ Aw +

Bw
⋅ To ⋅ ( τ + 1) +
Cw 2. (2
⋅ To ⋅ τ + τ + 1 + ) Dw 
2 3 2
 τ⋅ To 
Cdw = 67.571

Heat of vaporization:

∆Hvape := 38769.8 ∆Hvapw := 40683.1

Enthalpy:

∆H := −µme⋅ Cde⋅ ( T − To ) − ∆Hvape + −µmw⋅ Cdw⋅ ( T − To ) − ∆Hvapw

4
∆H = 4.811 × 10

Total heat leaving per time:

MWe := 46.069 MWw := 18.015 ρw := 998 ρe := 789

MWmix := µme⋅ MWe + µmw⋅ MWw ρmix:= µwe⋅ ρe + µww⋅ ρw

MWmix = 42.703 ρmix = 799.45

∆H⋅ Vd⋅ ρmix

∆Qd :=
MWmix

4
∆Qd = 3.466 × 10

∆Qd
∆Q :=
60

∆Q = 577.59
CONCLUSIONS

According to our energy balance, there is twice as much heat entering the cooling water
as is actually leaving the distillate. Our results should actually be reversed; we are more
likely loosing more heat from the distillate than enters the cooling water. After noting
that our cooling water energy balance is heavily dependent upon the cooling water
temperature change of only 7ºK, we realize that this has the potential for major error.
One explanation for the energy balance is that the cooling water is actually colder than
the column at ambient temperature. This means that the cooling water would be warming

11
even when no distillate is running through the condenser. If this is the case, then the
temperature change of the cooling water appears artificially high, resulting in an apparent
heat exchange that is higher than in reality.

Our data should be verified in the future with more runs. We have provided an energy
balance calculation module for future groups so that they can easily interpret their data.
Also, future groups may want to investigate the time dependence of distillate flow rate
and composition as these values also influence the validity of the energy balance.

12
REFERENCES

Crawford, Chan, Guo, Shell, and Ip. Binary Distillation of Ethanol and Water:
Improvements of Steady-State Operation and Measurement. Carnegie Mellon
University. 1999.

Geankoplis, Christie J., Transport Processes and unit Operations. Third Edition.
1993.

Zabetakis, Michael G., Flammability Characteristics of Combustible Gases. NITS. 68

13
Installation of a Steam Heat Exchanger to the
Rothfus Distillation Column Lab

Unit Operations Lab

Fall 2001: Team 7
Russell Ball
Lance Brown
Chaitra Hakkal
David Tucker
Abstract
This report discusses the design and implementation of a steam heat exchanger in
the reboiler of the Rothfus lab distillation column. The overarching goal of the project
was to improve safety and performance of the lab by replacing electric heaters with steam
heat exchangers. Using pressurized steam as the heat source, the heat exchanger design
goal was to heat up about 15 kg of water in less than 20 minutes. The heat exchanger
design made use of both heat exchanger and distillation column design equations. We
considered several different designs before deciding on the best choice of a coil within
the reboiler. The new heat exchanger satisfied the requirements we designed it to
perform. The startup heating time for the reboiler at a steam pressure of 25 psi was
approximately 11 minutes.
Introduction
Early in the semester our aspiration for this lab was to distill ethanol from a
water-ethanol mixture, but before this could happen we needed to repair the distillation
column and replace two electrical heaters with a steam-powered heater in the distillation
column reboiler. We did this because when the electric heaters failed, this could cause
flammable fluids such as ethanol to ignite. In addition the electrical system had some
problems with short-circuiting.
Our goals for this project were four-fold: (1) to replace the reboiler’s electric
heater with steam, (2) to repair the electrical system and make the distillation column
operational, (3) add a controller to the system, (4) and distill ethanol from water. We
were able to achieve the first two goals, but did not complete the rest due to time
constraints. After drafting and considering a few different designs, we settled on a heat
exchange coil within the reboiler.
The Chemical Engineering Department of Carnegie Mellon University
commissioned us to execute this work.
The background and theory section below discusses in greater detail the reasons
for replacing electric heaters, preliminary designs in general terms, and the final design.
The experimental section describes the equipment that went into our design and the
procedure involved in the actual production process. Results and discussion summarizes
the effectiveness of our improved design. Finally, recommendations outlines where
future groups with the distillation column lab should focus their efforts.

Background and Theory

Our initial design was to incorporate the external heat exchanger with the
distillation column. The large external heat exchanger would split into three parallel
streams: one for the reboiler, one for the feed, and one for the reflux (see Figure A1).
This design, however, would tie up a unit that is currently functioning as a stand-alone
lab station, and may require more heat than the unit can provide. Additionally, replacing
all three heat exchangers is a complicated task beyond reasonable time expectations of
what we could accomplish in one semester.
Our second design iteration was to use a new heat exchanger to perform the same
function, but only on the reboiler. We could have made this option work, but it would be
more expensive and more likely to break. The design required a pump to circulate the
bottoms fluid through the external heat exchanger (see Figure A2). Since the bottoms
fluid is near its boiling point, it could vaporize in the pump, causing the pump to fail.
Since this design offers no advantage over an internal heat exchanger, we opted for the
latter.
Throughout this design phase we developed heat duty calculations. Because heat
exchangers of various types are modeled similarly many of our calculations were
adaptable to changes in design. For final heat duty calculations see Appendices B
through E.
Because the unsteady state conditions are more demanding of a heat exchanger,
we based most calculations on maximum capability rather than minimum capability.
However, we confirmed that a steam pressure of 2 psi is adequately low to provide a
steady state heat duty for a variety of conditions. For example, in an ethanol-water system
anything below about 14 psi will not boil the heavy component.
The focus of our design effort then became how to incorporate an internal heat
exchanger coil in the reboiler. Challenges included how to disassemble the column,
developing a heat exchanger with high enough energy given the size restrictions, and how
to incorporate a controller.

Electrical Heaters
If not properly taken care of electrical heaters may fail and lead to a dangerous situation.
This happens as current running through the electrical wires generates heat and degrades
the wires?. If exposed wires are close enough, current can spark between them and ignite
ethanol (the fuel) as it comes it in contact with oxygen from the air.

Heat Exchangers
We had several design options in modeling the heat exchanger. Our initial plan called for
a 1-2 shell and tube heat exchanger. Baffles in the heat exchanger forces the steam to
flow across the tubes several times. The ethanol-water mixture in the tubes run parallel to
each other as the steam runs perpendicular. Temperature difference is calculated by the
log mean difference.

(Thi − Tco ) − (Tho − Tci )

∆Tlm = (Equation 1)
T − Tco
ln hi
Tho − Tci

Correction factor FT are is used to correct the mean temperature difference for a 1-2 heat
exchanger (Geankoplis, 270). So ∆Tm = FT∆Tlm, the overall heat transfer equation for the
heat exchanger becomes Q = UiAo∆Tlm = UoAo∆Tlm.

The preceding design assumes the heat exchanger is at steady-state. The design equation
is a function of time Q(t) = UAhx∆T(t) (Appendix C2). ∆T(t) is the difference between the
steam temperature and the water-ethanol mix.

Experimental
The actual experiment that involved data acquisition consisted of starting up the
column from room temperature two times. The purpose of these trial runs was to test the
effectiveness of the steam heat exchanger as a reboiler.
However, the main commitment of manpower was towards the building of the
reboiler unit. This section will primarily outline the equipment and steps involved in the
construction phase.

Equipment
• Hampden distillation column as available to us in September including:
• Failed electric heating unit
• Broken sight glass
 • Short circuit and other inadequacies of electrical function
• 3/8” stainless steel pipe, approximately 14 feet
• Steam conduit from building steam supply to distillation lab: 25 feet Swagelok 1/2” Teflon-
lined stainless steel braid flex hose
• Pressure regulator: bronze, 2-25 psi
• Swagelok fittings to
• Connect steam conduit to wall and pressure regulator
• Connect pressure regulator to coil connector piece
• Pass the coil connector piece through the right reboiler opening
• Connect the coil connector to the coil itself
• Pass the other end of the coil through the left reboiler opening
• Steam trap
• Oxalic acid

Procedure
Before the design phase could even come to an end, we needed to see inside the
reboiler so we would know what size the heat exchanger’s coils should be. We
disassembled the column by loosening the condenser so we could remove the trays.
After unscrewing all the bolts on the reboiler lid, we had to pry open the reboiler lid
because the rubber seal had firmly held it down.
The metal surface inside the reboiler was corroded. We mixed 250g of oxalic
acid crystals with water and left it in the reboiler to soak for a few days to remove the
corrosion. When we emptied the reboiler (and disposed of the acid by heavy dilution with
water) the metal inside was clean and smooth with little agitation required.
We designed the heat exchange coil based on the dimensions of the reboiler and
the locations of the level sensors. The 6” diameter was designed such that the coil would
rest in the main compartment of the reboiler rather than the narrower sunken region on
the bottom, and the coil would fit between the two level sensor posts. Russell Ball, Matt,
and Ken produced the coil in the machine shop by bending the 3/8” steel pipe tightly
around a metal cylinder attached to a lathe.
To complete the installation, we fit one end of the coil through the reboiler hole,
and then bent the other end so it could connect to the inlet piping. It was not possible to
have one continuous piece of metal go in one side and out the other.
We had to assemble the column in the same position as it was when removed, so
that the feed line would be inline with the column. Initially the column was offset by one
bolt position, which prevented us from continuing. After correcting the column, we
finished by connecting the pressure regulator and steam trap with Swagelok fittings.
The electrical system was shorted out so that turning on the main power caused
the circuit breaker to immediately shut the system down. We removed a number of wires
that were non-functional and replaced wires that were short-circuited. There was an
exposed wire that was touching the back of the circuit breaker. After removing this wire,
main power stayed on, but pumps were not interfaced yet. We only needed the feed
pump in order to test the reboiler function, so we wired that pump directly to external
110V power.
With the steam, the flow control system, and the feed pump all working, we
began testing the reboiler. The first attempt was with the pressure regulator set lower
than the factory-set 15 psi, to around 13 psi. Two days later, we ran the same experiment
with the maximum pressure setting for the pressure regulator, 25 psi. Stopwatches
recorded the time from when we turned on the steam to when the reboiler thermocouple
read near 2120F.

Results and Discussion

The installed steam heater succeeded in heating the reboiler within the
predetermined time frame. At an approximate pressure of 25 psi, the steam heated the
reboiler water from 59 ºF to 210 ºF in 11 minutes. This data corresponds well to the
model we predicted that assumed saturated steam at 30 psi and heating time in the
reboiler in of 7 minutes. The heat loss due to water vapor escaping the reboiler and
heating up the distillation column can account for the extra heating time. We expected
this type of deviation from our approximations, but we could not quantitatively account
for such a complicated system. In an attempt to correct for this error, we used a low
overall resistance value (U value) and used more pipe than our estimated length.
In a separate trial at a lower pressure, the heating time took 1 hour and 13
minutes. In this trial, the water temperature went from 59 ºF to a steady state temperature
of 206 ºF. This steady state temperature corresponds to a pressure of approximately 13
psi. During these trials, the column leaked a small amount of water through cracks in the
distillation column, which we fixed during the trials. Now, no visible leaks appear on the
column.
Although we successfully installed and operated the heat exchanger, we were not
able to install any type of automated control system, which was one of the initial goals of
our lab. Since the designs changed significantly from our original plans, we spent more
time than we expected designing the heat exchanger.
Another large problem that hindered our progress was the unavailability of
information and resources. As we talked with companies to gather information about
available products, we found that information we requestedwe requested of outside
sources was either slow to arrive or did not arrive at all. If we had more experience in
dealing with industry, we could have made faster progress in finding and ordering the
right parts and adapting to difficulties in communication.
We also lost time due to poor contingency planning. In some cases, our work
depended on parts being available. When parts were not available, we were unable to be
as productive as we would have liked to be.

Recommendations
• Order a valve control actuator and install it on the pressure regulator. We
recommend an actuator with a 4-20 mA input that is compatible with the existing
pressure regulator. (For more information on our recommended actuator, see ETI
reference.)
• For steam temperature data and control, install thermocouples in the Swagelok
fittings in the input and output streams of the heating coil.
• Rewire the feed, bottoms, and reflux pumps using wire with heat-resistant
insulation.
 • Order a new sight glass to replace the existing broken sight glass.
• Install new column tray seals to replace the existing seals, which have been
warped by heat and time.
• Create a permanent structural support for the pressure regulator.
• We assumed water as the heavy component when sizing the pressure regulator.
Any experiments that use a component that has a significantly lower vapor
pressure than water may need to resize the pressure regulator.
• Set up the computer interface and acquire more accurate data. Design a control
system and apply it to the distillation column. This would include control
apparatus and most likely a software component.
• Install a flow cell refractometer to measure real-time compositions of distillate
stream. Incorporate into control system.
• Test the control system using various chemicals and compositions.

Conclusion
The steam heat exchanger we designed works to our specifications. It meets
physical constraints of size, duty, and usability. We expect it to be reasonably
controllable with future modifications. It is relatively versatile with respect to future
needs of the column. Stainless steel is resistant to chemical corrosion, and the range of
heat duties is adaptable to various liquids.
The distillation column lab has many areas still that can be expanded and
improved by future lab groups.

References
ETI Electric Valve Actuators. Retrieved Dec. 17, 2001.
http://www.etisystems.com/valveactuator/index.html (talk to Dan when calling;
apologize for not getting back to him for a year or more; tell him you have a valve
you can send him so he can build the actuator for it)

Geankoplis, Christie J. Transport Processes and Unit Operations. Prentice Hall PTR,
1993. (design equations, steam condensing)

Perry, Robert H. Perry’s Chemical Engineering Handbook. 7 ed. McGraw Hill, 1997. (U
value, Pvap’s & Cp’s of ethanol and water)
 Appendix A

cooling water PC

distillate
TT 1

2 Steam
PT
trap

3 PC

TT feed
4
steam
Heat exchanger
5
PT Steam
Steam trap
6 trap
Cold water

TT
Reboiler PC

computer

PT
bottoms pump

Steam trap

Figure A1: Preliminary design using heat exchanger lab as main heat source. Steam line is split into
three heat exchangers. Temperature transmitters (TT) and pressure transmitters (PT) are fed into the
computer, which commands the pressure controls (PC) for each stream.
 7
TT

Reboiler PC

computer
steam
Heat exchanger PT

bottom pump
Steam
trap

Figure A2: Intermediate design with external heat exchanger. Proportional controls
(temperature and pressure) are incorporated for only the reboiler.

cooling water

refractometer
1
distillate
2

3
RT
feed
4

7
TT

Reboiler
PC

computer
steam
Steam PT
trap bottom

Figure A3: Final design with internal heat exchanger. Proportional

controls can be installed on the steam line. Refractometer transmitter
can be installed to gather real time distillate composition data.
Appendix B: Design parameters

400⋅ BTU
U := Heat transfer coefficient
2
hr⋅ ft ⋅ R

Rreflux := 5 Reflux ratio

gm Feed flowrate
Feed := 100⋅
min

xfeedmEA := 0.5 Mass fraction of feed that is ethanol

TinW := ( 273 + 10) ⋅ K Water inlet temperature

Dcoil := 4⋅ cm
Diameter of condenser coil

n turns := 60
Turns of the condenser coil

Dtube := .25⋅ in Diameter of the condenser tubing

L
M condW := 2.4⋅ ⋅ρ W Mass flow of condensing water
min
lb
Fstm := 10⋅ Mass flow of steam
min

Rboilup := 5 Boilup ratio

Volreb := 16L Volume of the reboiler

Pstm := 30⋅ psi Steam pressure

Tstm ( Pstm ) = 394.475K Steam temperature as a function of steam pressure

Appendix C1: Temperature model in reboiler
Tw( t) :=  298⋅ K −  ⋅ exp( −p⋅ t) + r
r
 p p
where p and r are simply constants of the system:
U⋅ A hx U⋅ A hx⋅ Tstm
p := r := −3 K
Volreb⋅ ρ W⋅ CpW Volreb⋅ ρ W⋅ CpW p = 3.713 × 10 Hz r = 1.465
s

400
387.818

376

352

Tw ( t )

328

304

298 280
0 100 200 300 400 500 600 700
0 t 720

Appendix C2: Heat exchange vs. time

q hx( t) := U⋅ A hx⋅ ∆T( t )

where ∆T( t) := ( T stm − Tw( t) )

25
23.983

20

15
q hx ( t )
1000
10

3.746 0
0 100 200 300 400 500
0 t 500
Appendix D: Calculation of condenser heat load
Fcond := ( Rreflux + 1) ⋅ FnEA <--assuming negligible W in vapor stream

Qreqd cond := ∆HvapEA ⋅ Fcond

Qreqd cond = 4.277kW

(
A cond := π⋅ Dcoil⋅ n turns ⋅ π⋅ Dtube ) estimate ToutW := ( 273.15 + 40) ⋅ K

Qcond := ( TinW − ToutW) ⋅ CpW⋅ M condW

Qcond = −5.046kW
Appendix E: Steam pressure-temperature lookup charts

440

420
T chart

400
K
380

360
0 20 40 60 80 100 120 140
Pa
Pressure
P chart ⋅ in psi
psi
4
4.1 .10

4
4 .10

4
3.9 .10

∆Hvap chart
4
3.8 .10

kJ/mol
4
3.7 .10

4
3.6 .10
0 20 40 60 80 100 120 140
Pa
P chart ⋅ in psi
Pressure
psi
Appendix F: Experimental data
Steam pressure Steady state temperature Startup time
13 psi 206 degrees F 1 hr, 13 min
25 psi 212 degrees F (boiling point) 11 min
Batch Distillation: An Energy Balance
Scott Cunning
Lauren Petruzzi
Jason Stieg

Carnegie Mellon University

Unit Operations Lab
October 20, 2000
Abstract
A complete energy balance was performed on the batch distillation column. It was
determined that the difference between inlet and outlet power converges to zero as the
distillation progresses. The difference in the energies can be accounted for by an
accumulation term. This accumulation occurs in the heating of the column. It was
determined that 85% of the heat loss occurs in the cooling water, and 15% is due to heat
loss to the atmosphere.
Introduction

Batch distillation is usually used when the initial feedstock to the distillation column is
not available on a continuous basis. One reason for this could be due to the production of
a by-product feedstock from a previous batch process. In batch distillation, liquid is
charged to a heated kettle. There it is heated slowly to boil. The resulting vapors are
withdrawn as soon as they form to a condenser, where the distillate is collected. The
condenser at the top of the column aids in cooling the vapor stream to produce a saturated
liquid. In the case of ethanol and water, the first portion of vapor condensed is richest in
ethanol. As the process continues the more volatile component, ethanol, will dominant
the vapor, while the liquid will be predominantly composed of the less volatile
component, water.

The purpose of this lab was to perform an energy balance on a six-tray batch distillation
column of ethanol and water. Through this heat balance, heat losses were determined at
various points throughout the apparatus. To perform this balance, the distillation column
was modeled as two cylinders. The first cylinders included the six trays. It was
separated into six sections, each one representing a tray with a uniform temperature. To
account for the heat lost between the column (cylinder 1) and the surrounding air natural
convection was assumed. From our column modeled as a vertical cylinder and a
calculation of the Prandlt, Nusselt, and Grashof numbers, the heat transfer coefficient and
therefore the rate of heat lost was determined. To simplify the calculations for the heat
transfer to the air each section was assumed to be all glass with negligible internal
resistance.

The second cylinder was the overhead condenser in which the cooling water ran through
to condense the distillate vapor into a saturated liquid. The boiler was assumed to be well
insulated and the end effects on the cylinders were assumed negligible. To determine the
pressure in the overhead cylinder a couple of assumptions were made. At a specific time,
when the temperature was 203° F the compositions were assumed to be 90 mol% ethanol
and 10 mol% water. Using this temperature and the dew point calculation,

Σ(yk/αk/n) = Pn°/P

the pressure in the condenser was calculated. This pressure was then assumed to remain
constant so that the other compositions could be back calculated. The compositions and
the temperature changes allowed for the heat losses to be determined.
Procedure

In order to collect distillate, it was necessary for the column to heat up. As vapor rose
through the column, the trays were heated by the vapor’s condensing. Once a tray
reached the dew point temperature, the vapor could proceed up the column to the cooling
coil. The times at which the trays began heating and their equilibrium temperatures were
recorded on LabView. At the cooling coil, condensate was collected on the coil as
distillate. We measure the distillate flow rate manually with a stopwatch and volumetric
flask.

Results and Discussion

The objective was to perform a complete energy balance over the entire column. Using
LabView, data was taken from the column and formulated into tables. Distillate flow rate
data was taken by hand. This data was used in calculations to determine the energy
balance. Due to problems with the apparatus, it was only possible to take data during one
lab session, yielding one trial.

It was assumed that the input of heat to the system was soley due to the heater in the
boiler. Also, it was assumed that heat left the system only through the cooling water and
heat loss to the surrounding air. The calculation for the input power is represented by the
following:

P= IV = (11 A)(220 V) = 2.42 kW

It was assumed that the power input was constant for the entire distillation. The
calculation for the heat loss in the cooling water is represented by the following:

Q = mCp(Tout-Tin)

Where m is the mass flow rate of water, the heat capacity, Cp, was assumed to be a
constant of 4.184 KJ/Kg*K, and Tout and Tin represent the outlet and inlet water
temperatures respectively. For the heat loss to the surrounding air the column was
modeled as a vertical cylinder undergoing natural convection. The heat transfer
coefficients were determined through the following equation.

h = 1.37(∆T/L)1/4
The relationship between power in and power out is shown in Figure 1.
Energy Balance on Column

2.5

2
Power kW

Power Out
1.5
Power In

0.5

0
0 500 1000 1500 2000 2500 3000 3500

TIme (sec)

Figure 1. Power in and Power out vs. Time Initially there is a large difference in the power
coming in and the power exiting. However, as the column heats up and the distillation process nears its
end the power leaving the column approaches the power going into the column exponentially.

The power leaving the distillation column begins low because the column has to allowed
to heat up first. As the six trays reach their dew points and the vapor moves its way up
the column the power increases as well. Once all the trays are heated and distillate is
being collected, the power gets closer to the value inputed into the system.

It is important to note that the heat loss is dominated by heat loss through the cooling
water. An average of 85% of the heat loss occurs through the cooling water. This leaves
15% to be accounted for by loss through natural convection of the column. To complete
the balance the difference in input and output power must be accounted for.
 Energy In -Energy Out

2.5

2
Power kW

1.5

0.5

0
0 500 1000 1500 2000 2500 3000 3500

-0.5

Time (sec)

Figure 2. Energy Balance Over Time The difference of energy in minus energy out is plotted
versus time. This depicts the amount of energy lost through the column during the process. Initially a lot
of energy is being lost because not enough power is being generated by the column. As the process nears
completion the accumulation term decreases.

Initially the distillation column starts at room temperature. It must be heated so that the
vapor can reach the top of the column. Heat is therefore accumulated in the column. The
total amount of heat accumulated during the process is equal to the area under the curve
in Figure 2. The difference in energies decreases as time increases, showing that the
column is no longer accumulating heat. The column has reached the same temperatures
of the vapor inside, resulting in greater amounts of energy.

An attempt was also made to complete an energy balance of the condenser at the top of
the column. The balance was made on Q of the cooling water vs. the Q of the distillate.
Both latent and sensible heat effects were taken into consideration for the calculation of
the distillate. It was determined that the cooling water was absorbing 7 times more heat
than the distillate was loosing. There are a number of reasons why these calculations
may be off. To determine our heat of vaporization the distillate compositions had to be
calculated. A number of assumption were made, such as constant pressure and initial
compositions, so that the compositions could be determined through dew point
calculations. Also, there could be errors in the readings from the thermocouples or a
general problem with the apparatus.

Conclusion

In conclusion, we recognize that this is only a crude estimation of the heat balance on this
distillation column. In the future we suggest that more than one trial be conducted so that
replica data is available to back up calculations. Also, better assumptions should be made
when calculating distillate compositions. Future groups may want to concentrate on
determining the problem with the cooling water balance. For instance, why the cooling
water is apparently absorbing so much energy from the system.
References

Abbott, M.M., Smith J.M., Van Ness, H.C. Introduction to Chemical Engineering
Thermodynamics. McGraw Hill Company: New York, 1996.

Beigler, Lorenz T., Grossman, Ignacio E., Westerberg, Arthur W. Systematic Methods of
Chemical Process Design. Prentice Hall:Upper Saddle River, 1997.

Crawford, Chan, Guo, Shell, and Ip. Binary Distillation of Ethanol and Water. Group 3,
Fall 1999.

Geankoplis, Christie J. Transport Processes and Unit Operations. Prentice

Hall:Englewood Cliffs, 1993.
Appendix A. - Nomeclature

A = area
Ak = Antoine coefficient
Bk = Antoine coefficient
Ck = Antoine coefficient
Cp = heat capacity
g = gravity
h = heat transfer coefficent
k = thermal conductivity
L = length
NGr = Grashof number
NPr = Prandlt
P = pressure
P° = partial pressure
q = heat-transfer rate
T = temperature
yk = composition of the distillate
αk/n = P°k/ P°n
β = volumetric coefficient of expansion
µ = viscosity
ρ = density
Appendix B. - Calculations

NGr = L3ρ2gβ∆T/µ2

NPr = Cpµ/k

NNu = hL/k = a(NGrNPr)m

h = 1.37(∆T/L)1/4

q = hA(Tw – Ta)

Pok(T) = exp(Ak – Bk/(Ck + T))

P = αavgPok(Tbub)/αk/n

P= Pon(Tdew)/Σ(yk/αk/n)

A = 2πrL
Appendix C. – Graphs

Temp vs Time all Trays

250

200

Tray 6T
150
Tray 5T
Temp (F)

Tray 4T
Tray 3T
Tray 2T
100 Tray 1T
Tray 0T

50

0
0 500 1000 1500 2000 2500 3000 3500
Time (s)

Figure C1. – Temperature of all Trays vs. Time

Tcw vs Time

120

100

80
Temp (F)

Cooling Out
60
Cooling In

40

20

0
0 500 1000 1500 2000 2500 3000 3500
Time (s)

Figure C2. – Temperature of the Cooling Water vs. Time

 Tboiler vs. Time

215

210

205
Boiler Temp

200 Boiler Temp

195

190

185
0 500 1000 1500 2000 2500 3000 3500
Time

Figure C3. – Temperature of the Boiler vs. Time

Energy Balance on Column

2.5

2
Power kW

Power Out
1.5
Power In

0.5

0
0 500 1000 1500 2000 2500 3000 3500

TIme (sec)

Figure 1. – Energy Balance on Distillation Column

 Energy In -Energy Out

2.5

2
Power kW

1.5

0.5

0
0 500 1000 1500 2000 2500 3000 3500

-0.5

Time (sec)

Figure 2. –Energy Difference vs. Time

Study of Distillation for Octanol, Water, and Ethanol for use
with a LLE Column
Estelle Burri
Yvonne Chen
Penny Tan
John Velicevich

Group 10

December 10, 1999

 Abstract

The purpose of this lab was to determine the conditions necessary to distill a mixture of

octanol, water, and ethanol that comes from a LLE column. To do this we ran batch

distillation experiments at 1 atm using different feeds of unknown composition. The

approximate composition was a 30:25:45 ethanol:octanol:water. The GC results show

that there was no octanol in the distillate stream at a temperature of ~180 F and other

groups data showed that there was no ethanol in the bottoms. From this data we

recommend using the above conditions to combine the LLE and distillation column.
Background

Distillation is a common method for the separation of production streams in

industry. A distillation column acts like a series of equilibrium flash tanks stacked in a

column. The reboiler vaporizes part of the bottoms liquid stream and the vapor stream is

sent up through the column. The vapor stream is mixed with the liquid stream moving

down the column and allowed to reach equilibrium. The vapor stream then enters the

condenser where it is cooled to a liquid and sent to a holding tank. Part of the liquid can

then be sent back to the column to mix with the vapor phase.

If the stream is to remain in the liquid phase, another method of separation is

liquid liquid extraction. In this case one liquid phase stream containing the desired

component is contacted with an immiscible liquid. The key component will be

transferred to the other liquid, which can be easily separated by a different means.

Introduction
The purpose of this lab is to separate a ternary mixture of ethanol, water and

octanol from the liquid liquid extraction column into two streams that can be returned to

the LLE column. The feed stream is approximately 30% ethanol, 25% 1-octanol, and 45%

water. The distillate phase from the distillation column was a mixture of ethanol and

water while the bottoms product was a two-phase mixture of water and octanol. We have

conducted our experiments using batch distillation. Our distillate products were analyzed

using a gas chromatograph (GC.) In what follows, we present our procedure, the results,
 Collected the distillate

Run #2
Used the bottoms product as feed
Ran the distillation column
Collected the distillate

Run # 3
Used the bottoms product and added more ethanol and water mixtures as feed.
Ran the distillation column
Collected the distillate.

Run #5
Used what was already in the feed tank without adding anything.
Ran the distillation column
Collected the distillate.

Results
Injection B Injection C Injection D Injection E Injection F
T of distillate(degrees F) 171 171 172.5 172.5 172.5
Water 0.708 0.778 0.209 0.4268 0.47
Ethanol 2.788 2.419 1.155 2.86 2.83
%water 20.3 24.3 15.3 13 14.2
Run number one Run number two

Injection G Injection H Injection I Injection J

T of distillate(degrees F) 173.6 173.6 178 178
Water 0.535 0.551 1.255 1.326
Ethanol 2.9 2.92 2.2 2.126
%water 15.6 15.9 36.3 38.4
Run number three Run number five
Table 1.Results from the distillate. This shows that no octanol is present, and only a mixture of water and
ethanol.

Discussion
Since the temperature of the distillate is slightly higher we expect the percentage of water

to increase slightly. Instead, the percentage of water decreased. However, the rest of the

data agreed with our expectations. In our analysis of the distillate stream, we see that the

ethanol and water mixture follows the Txy curve fairly well. Since there are impurities in

the system, the Txy curve should be treated only as an approximation. Our data for the

distillate stream is similar to that of the other groups’data. We therefore assume that

since they have no ethanol in the GC analysis of their bottoms product, and we have

observed our bottoms product to split into a two-phase mixture, we can safely assume

that the amount of ethanol in the bottoms stream is negligible.

From the relative volatilities, we see that there is not going to be any octanol in

the distillate. The water is split into the distillate and bottoms stream, and since ethanol’s

relative volatility is higher than the light key, we can assume that all the ethanol will be

found in the distillate. If the feed composition were to change so that it contained a

higher percentage of water we would expect the flowrate for the distillate to decrease.

Since there is less ethanol in the system and the temperature would remain nearly the

same the flowrate will decrease. On the other hand if the amount of ethanol in the feed

increases compared to the amount water then the flowrate of distillate will increase.

Conclusions

Based on the results we feel that the system will be able to be connected to the
separate the two phase mixture of water and octanol before the octanol stream is sent

back to the LLE column.

Future work will be to determine the exact feed compositions that will be entering

the column from the LLE and to optimize the flowrates to be used in the LLE.

References

Biegler, L.T. et al, Systematic Methods of Chemical Process Design. Prentice

Hall, NJ. 1997.

Brunsell, J, et al. “Liquid-Liquid Extraction Using the Force.” Group 6, 1999